Reaction Mechanisms during Atomic Layer Deposition of AlF3 Using Al(CH3)3 and SF6 Plasma

Metal fluorides generally demonstrate a wide band gap and a low refractive index, and they are commonly employed in optics and optoelectronics. Recently, an SF 6 plasma was introduced as a novel co-reactant for the atomic layer deposition (ALD) of metal fluorides. In this work, the reaction mechanisms underlying the ALD of fluorides using a fluorine-containing plasma are investigated, considering aluminum fluoride (AlF 3 ) ALD from Al(CH 3 ) 3 and an SF 6 plasma as a model system. Surface infrared spectroscopy studies indicated that Al(CH 3 ) 3 reacts with the surface in a ligand-exchange reaction by accepting F from the AlF 3 film and forming CH 3 surface groups. It was found that at low deposition temperatures Al(CH 3 ) 3 also reacts with HF surface species. These HF species are formed during the SF 6 plasma exposure and were detected both at the surface and in the gas phase using infrared spectroscopy and quadrupole mass spectrometry (QMS), respectively. Furthermore, QMS and optical emission spectroscopy (OES) measurements showed that CH 4 and CH y F 4- y ( y ≤ 3) species are the main reaction products during the SF 6 plasma exposure. The CH 4 release is explained by the reaction of CH 3 ligands with HF, while CH y F 4- y species originate from the interaction of the SF 6 plasma with CH 3 ligands. At high temperatures, a transition from AlF 3 deposition to Al 2 O 3 etching was observed using infrared spectroscopy. The obtained insights indicate a reaction pathway where F radicals from the SF 6 plasma eliminate the CH 3 ligands remaining after precursor dosing and where F radicals are simultaneously responsible for the fluorination reaction. The understanding of the reaction mechanisms during AlF 3 growth can help in developing ALD processes for other metal fluorides using a fluorine-containing plasma as the co-reactant as well as atomic layer etching (ALE) processes involving surface fluorination.